This study focused on the study of titanium sites, their local structure and reactivities in nanoporous titanosilicates frameworks by using in situ X-ray absorption spectroscopy. XANES provides the information on the oxidation state of the titanium species as well as their change in coordination geometry during de- and re-hydration. Results from in situ XANES studies shows that TS-1 is much more hydrophobic than TiAl or TiFe systems. Pre-edge features of Ti K-edge XANES spectra of these materials also suggested that TiIV is the dominant Ti coordination in dehydrated system whilst TiVI is the dominant in the re-hydrated one.